Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G67/00—Macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing oxygen or oxygen and carbon, not provided for in groups C08G2/00 - C08G65/00
  • C08G67/02—Copolymers of carbon monoxide and aliphatic unsaturated compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0025—Crosslinking or vulcanising agents; including accelerators

Definitions

• This invention relates to a thermoset resin, to a process for its preparation, to various uses thereof, and to a precursor composition of the resin.
• thermosetting resin compositions are increasingly employed as materials of established commercial utility. They find their use for example in the automotive, lacquer, paint, and coating industry, and as various castings in small house-hold appliances. However, their use is not limited to these applica­tions, as research is still developing new fields of application. To satisfy clients' wishes a range of resin compositions must be available in which the resin corresponding to the particular needs can be found. For instance, in the lacquer, paint, and coating industry resins are requested to have features such as good adhesion, temperature stability, chemical and stress resistance. Moreover, the thermosetting compositions should have a good processability and preferably be made of cheap and common starting materials.
• thermoset resins or resin compositions from thermoplastic material, e.g. oligo­mers or polymers (further collectively referred to as "polymers"), by curing.
• the curing may consist of e.g. a heat treatment, of an (ultraviolet) light treatment, or of a chemical reaction, using a so-called curing agent.
• the curing treatment generally causes some chemical modification of the molecules of the polymer, usually crosslinking between chains. The latter im­plies that bridges between chains are made, and when a chemical curing is effectuated, this often means that reactive groups of the molecule of the curing agent link themselves to reactive sites on the polymer chain.
• the molecules of curing agents generally con­tain at least two reactive groups, the result is forma­tion of a bridge incorporating (a part of) the curing agent's molecule.
• agents containing two or more alkoxy groups react with polymer chains con­taining hydroxyl, carboxyl or amide groups, under formation of crosslinked polymers and an alkanol.
• thermosets Although many commercial thermosets have excellent properties, they are sometimes rather costly, which may be due to the prices of the polymers from which they are prepared. Moreover, some of them are not very handleable, i.e. they are either not liquid at room temperature (mixing thus being inconvenient), or not miscible with the curing agent, or not processable in other respects.
• novel thermoset resins may be prepared from novel thermosetting resin compositions, which compositions comprise a curing agent and a linear, alternating "polyketone” or a functional derivative thereof, which resins are easily processed, present excellent physical and chemical resistance, and are made from inexpensive starting materials such as carbon monoxide and ethene.
• EP-A-118312 discloses a chemical curing of polyketones, but the polyketones used and intended therein do not have a linear, alter­nating structure (instead, they should rather be looked upon as polyolefins having a relatively small number of carbonyl groups randomly dispersed in the polymer backbone), which yields quite different physical and chemical properties.
• the present invention accordingly relates to a thermoset resin obtainable by curing a thermoplastic polymer, characterised in that the resin is obtainable by reacting a curing agent with a linear alternating copolymer of carbon monoxide and one or more olefinic­ally unsaturated compounds, or with a curable function­al derivative thereof.
• thermoset resin as claimed above, characterised in that a curing agent is reacted with a linear alternating copolymer of carbon monoxide and one or more olefinically unsaturated compounds, or with a curable functional derivative thereof.
• thermosetting composi­tion comprising a curing agent and a thermoplastic polymer, characterised in that it comprises as the thermoplastic polymer a linear alternating copolymer of carbon monoxide and one or more olefinically unsaturat­ed compounds, or a curable functional derivative thereof.
• the handleability of polymers is closely related to their viscosity, and thus to their molecular weight.
• Polyketones of low molecular weight are liquid or viscous, and can thus be blended easily with the curing agent, and the resulting thermoset resins are usually liquid or viscous as well, which simplifies their application as a coating or an adhesive.
• resins of high molecular weight may be used as coatings etc. too, by applying them as a powder, e.g. by elec­trostatic or flame spraying techniques.
• the weight average molec­ular weight of the thermoplastic polymer from which the resin is obtainable is below 200,000 daltons, espe­cially in the range of 200 to 20,000 daltons, and in particular in the range of 200 to 10,000 daltons. It makes some difference for the viscosity whether the thermoplastic polymer from which the present thermoset resins are obtainable, is a "pure" polyketone or a derivative thereof, and in as much as necessary, this will be addressed at the appropriate places hereafter.
• A′ stands for the ethylene biradical of formula -CH2-CH2-.
• suitable compounds A are olefinically unsaturated hydrocarbons such as olefins or styrenes, and unsaturated non-hydrocarbons, such as acrylic acid or methacrylates.
• the one or more olefinic­ally unsaturated compounds, being monomers of the thermoplastic polymer from which the resin is obtain­able are selected from alkenes, cycloalkenes, arylalk­enes, alkadienes and oxycarbonylalkenes, having from 2 to 12 carbon atoms. It is particularly preferred that the one or more olefinically unsaturated compounds, being monomers of the thermoplastic polymer from which the resin is obtainable, comprise at least ethene.
• A is a hydrocarbon, especially of up to 12 carbon atoms, in particular an alkene of up to 8 carbon atoms such as: ethene, propene, butene, pentene, methylbutene, hexene, methylpentene, dimethylbutene, ethylbutene, heptene, methylhexene, dimethylpentene, ethylpentene, trimethylbutene, ethylmethylbutene, octene, methylheptene, dimethylhexene, ethylhexene, trimethylpentene, ethylmethylpentene, propylpentene, dimethylethylbutene, diethylbutene, and methylpropyl­butene. More preferably A is a 1-alkene, ethene or propene being most preferred.
• the compound B may be any ethylenically unsaturat­ed compound other than A.
• B is a compound selected from alkenes, alkadienes, cycloalkenes, e.g. cyclopentene or cyclohexene, aryl substituted alkenes, e.g. styrene or p-methylstyrene, carbonyloxy substi­tuted alkenes, e.g. acrylic acid, crotonic acid, maleic acid, maleic acid anhydride, fumaric acid, or mono­methyl fumarate, or other vinyl-type monomers, such as vinyl chloride, or acrylonitrile. More preferably, B is selected from 1-alkenes, or aryl-substituted 1-alkenes.
• Very suitable polyalcohols are polyalcohols having a molecular weight of from 450 to 3500 and preferably of from 1000 to 1500.
• thermoplastic polymer from which the resin is obtainable is a linear alternating copolymer of carbon monoxide and one or more olefinic­ally unsaturated compounds.
• the ther­moplastic polymer is cured as such, without further derivatisation.
• thermoplastic polymer from which the resin is obtainable is a curable functional derivative of a linear alternating copolymer of carbon monoxide and one or more olefinically unsaturated compounds.
• Suitable curable functional derivatives of poly­ketones to be employed in the present invention com­prise, in principle, all derivatives of ketone carbonyl groups which contain a function capable of reacting with a curing agent. They are selected, inter alia, from the group comprising polybisphenols, acrylonitrile derivatives, polyaminoacids, Mannich addition products, polythiols, dithiocyclic group substituted polyketones, hemimercaptals, polyamides, polyamines, furan deriva­tives, polycyanohydrins, polyoxims, polyphosphonates, polyvinylketones, polyhydroxymethylketones, polyamino­alcohols, polyketone ketals and hemiketals, polyepoxide derivatives, polyhydroxysulphonate adducts, polyhydr­oxyphosphonate adducts, polydihalo derivatives, poly­haloketone derivatives, polyhydrazone derivatives and polyalcohol
• the polyalcohols are obtainable by catalytic reduction of the polyketone with hydrogen gas, or by reduction with sodium borohydride or lithium aluminium hydride in either hexafluoroisopropanol, tetrahydro­furan, or any other suitable solvent.
• the degree of reduction i.e. the percentage of hydroxy groups formed by reduction related to carbonyl groups originally present, is preferably from 4 to 100 %, more preferably from 20 to 100 %, most preferably from 50 to 100 %.
• the curable functional derivative of the copolymer is a polyalcohol. It is preferred that the polyalcohol has a weight average molecular weight of from 450 to 3,500, especially from 1,000 to 2,000.
• thermosetting composition comprising a curing agent and a thermoplastic polymer, character­ised in that it comprises as the thermoplastic polymer a linear alternating copolymer of carbon monoxide and one or more olefinically unsaturated compounds, or a curable functional derivative thereof.
• thermoplastic polymer character­ised in that it comprises as the thermoplastic polymer a linear alternating copolymer of carbon monoxide and one or more olefinically unsaturated compounds, or a curable functional derivative thereof.
• Such composi­tions can be marketed as one-component systems, which are storage-stable for periods of several minutes up to several months or possibly years, depending on temperature and on the choice of components, or as two-component systems.
• Curing agents suitable for the preparation of the resins of the invention are compounds able to react with the (derivatised) carbonyl groups of different (modified) polyketone chains, thereby forming a highly crosslinked, three-dimensional network.
• suitable compounds are di- and polyaldehydes, di-­and polyamines, ammonia, ammonium salts, di- and poly­acids, di- and polyepoxides, di- and polyisocyanates, anhydrides, aminoplast resins, and adducts and precur­sors of these compounds.
• the amount of curing agent to be added to the polymer is from 0.1 to 10, preferably from 0.2 to 5, more preferably from 0.25 to 1.1 mole per mole of polymer. Expressed in weight percentages, the amount is in most cases more than 3% by weight, preferably from 7 to 120 %wt and in particu­lar from 20 to 100 %wt, based on the weight of the thermoplastic polymer.
• the degree of cure is also controlled by the curing temperature; i.e. with a curing temperature of 125 °C or above, less agent is required to obtain sufficient cure, than with a curing temperature of 100 °C. There is no upper limit to the amount of curing agent, though above a certain level it is no longer economical to use more, or even disadvan­tageous to the properties of the final product.
• the curing agent preferably is either a primary di- or polyphosphine, a primary di- or polyamine, an adduct or precursor of an aforementioned compound, a compound having in combination two or more of the aforementioned functional groups, ammonia or an ammonium salt. More preferably the curing agent is a primary di- or polyam­ine, such as ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethyl­enepentamine, phenylenediamine, methylenedianiline, dimethylpropylenediamine, melamine, or the like. Also preferred are carbamate adducts or metal complexes thereof, e.g.
• a most preferred curing agent for linear, alternating polyket­ones is diethylenetriamine.
• the quantity of curing agent is suitably from 0.1 to 10 mole per mole of copolymer.
• the curing agent pref­erably is a di- or polyacid, a di- or polyamine, a di-­or polyepoxide, a di- or polyisocyanate, an anhydride, an aminoplast resin, or an adduct or precursor of these compounds. It will be obvious to the skilled reader which agent to select for a particular derivative.
• the amino­plast resins such as alkoxylated or aryloxylated reaction products of formaldehyde and melamine (2,4,6-­triamino-s-triazine) or benzoguanamine (2,4-diamino-6-­phenyl-s-triazine) are preferred.
• Other preferred curing agents for polyalcohols are the optionally alkylated melamine-formaldehyde resins, of which hexakis­methoxymethylmelamine (HMMM) is particularly efficient.
• a quantity of more than 3 %wt of a curing agent based on the weight of the polyalcohol constituent in the resin composition, in particular of from 7 to 120 %wt of a melamine-formaldehyde resin, and especially of from 20 to 100 %wt of hexakismethoxymethylmelamine as the curing agent has been found to be very effective.
• thermosetting resin composition may also comprise co-reactants that can be built-in to modify the properties of the thermoset final product.
• co-reactants are di- or polyalcohols such as ethylene, propylene, and trimethylene glycol, cyclopentanediol, glycidol, gluticol, ribitol, erythrol, threol, and pentaerythritol.
• the resin compositions can be cast, moulded, extruded, pultruded, laminated, and they may serve as binder compositions in paints, lacquers, stoving enam­els or the like. Moreover, to the resin compositions stabilisers, plasticisers, lubricants, colouring and enforcing agents, or fibres can be added without di­verging from the gist of the invention.
• the invention also relates to a process for coating or bonding an article by applying a quantity of thermosetting resin thereto, characterised in that a thermosetting composition as defined herein­before is applied, as well as to an article of manufac­ture, characterised in that it consists at least in part of a thermoset resin according to the invention.
• a linear alternating carbon monoxide/propene copolymer was prepared as follows.
• a mechanical stirred autoclave with a volume of 1000 ml was charged with 250 ml methanol, 106 mg Cu(II)tosylate, 120 mg 1,3-bis(di­phenylphosphino) propane, and 54 mg Pd(II)acetate.
• the autoclave was closed, flushed and pressurised with carbon monoxide to a pressure of 60 bar, after which 100 g of (liquid) propene was added to the contents of the autoclave. The pressure was then brought to 40 bar by expanding carbon monoxide.
• a polyalcohol was prepared by adding a solution of 2 g of the polyketone prepared in Experiment A in 25 ml THF drop-wise to a stirred suspension of 1 g LiAlH4 or NaBH4 in 10 ml THF. After addition, the mixture was refluxed for 18 hours. Water was added, and the mixture was filtered. Chloroform was then added and the organic layer separated, extracted with water, dried over MgSO4, and filtered. The product was obtained by evapo­ration of the solvents. The polyalcohol mixture was a viscous ochre coloured liquid.
• a black and brittle coating was prepared by depos­iting a thin film (essentially 0.050 mm) of the poly­ketone prepared in Experiment A on a phosphated steel strip, and placing the strip in a temperature oven set at 160 °C for 40 min. After cooling the degree of cure was qualitatively assessed by subsequently rubbing with a wad soaked in methylethyl ketone (MEK) and scratching with a pencil or knife (Pencil hardness, as defined in ASTM D3363-74). The crosslinked oligomer withstood less than 10 MEK rubs, and performed poor in the scratch test.
• MEK methylethyl ketone
• a hard, tough and light brown coating was prepared by depositing a thin film of the polyalcohol prepared in Experiment C on a phosphated steel strip, and plac­ing the strip in a temperature oven set at 190°C for 90 min. After cooling the cure was quantitatively assessed by subsequent rubbing with a wad soaked in methylethyl ketone (MEK) and scratching with a pencil or knife (Pencil hardness, as defined in ASTM D3363-74). It appeared that the sole polyalcohol crosslinked in air to form a coating resisting more than 100 MEK rubs.
• MEK methylethyl ketone
• a hard, tough and clear coating was prepared according to the directions set out in Example 1 using 25 %wt of HMMM based on the weight of the polyalcohol and a drop of concentrated HCl. By heating at 140 °C for 60 min in a nitrogen atmosphere a 0.025 mm thick film was obtained that withstood more than 100 MEK rubs and performed well in the pencil hardness test (i.e., no visible scratch with H4 pencil).
• Hard, tough and clear coatings were prepared according to the directions set out in Example 1 using different amounts of HMMM per mole polyalcohol, option­ally a drop of surfactant to eliminate strain induced by temperature differences, and curing the resin compo­sition for 60 min in a nitrogen atmosphere at tempera­tures ranging from 75 to 150 °C.
• Example 3/0 is presented as a comparison.
• the 0.025 mm thick films of Examples 3/1, 3/2, 3/3 and 3/4 performed well in the pencil hardness test.
• the MEK resistance results are summarised in the Table below.
• a hard, tough and ochre coating was prepared according to the directions set out in Example 1, using 1.1 mole of diethylenetriamine per mole oligomer as curing agent. At approximately 200 °C for 90 min. in a nitrogen atmosphere, a 0.100 mm thick film was obtained that withstood more than 100 MEK rubs and performed well in the scratch test (i.e., no visible scratch with H4 pencil).
• a hard, tough and black coating was prepared according to the directions set out in Example 1, using 0.25 mole of diethylenetriamine per mole oligomer as curing agent. At approximately 190 °C for 90 min. in air, a 0.050 mm thick film was obtained that withstood more than 100 MEK rubs and performed well in the scratch test (H4).

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Polyethers (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Reinforced Plastic Materials (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Laminated Bodies (AREA)
• Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
• Paints Or Removers (AREA)
• Encapsulation Of And Coatings For Semiconductor Or Solid State Devices (AREA)
• Processes Of Treating Macromolecular Substances (AREA)
• Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
• Adhesives Or Adhesive Processes (AREA)
• Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)

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Cited By (24)

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• 1989
  • 1989-11-07 KR KR1019890016096A patent/KR0163029B1/ko not_active Expired - Fee Related
  • 1989-11-07 DE DE68926218T patent/DE68926218T2/de not_active Expired - Lifetime
  • 1989-11-07 AT AT89202833T patent/ATE136563T1/de not_active IP Right Cessation
  • 1989-11-07 ES ES89202833T patent/ES2085860T3/es not_active Expired - Lifetime
  • 1989-11-07 EP EP89202833A patent/EP0372602B1/fr not_active Expired - Lifetime
  • 1989-11-08 NO NO894452A patent/NO176965C/no not_active IP Right Cessation
  • 1989-11-08 JP JP1290951A patent/JP3003115B2/ja not_active Expired - Lifetime
  • 1989-11-08 DK DK558289A patent/DK558289A/da not_active Application Discontinuation
  • 1989-11-08 AU AU44490/89A patent/AU620168B2/en not_active Ceased
  • 1989-11-09 CN CN89108449A patent/CN1032140C/zh not_active Expired - Fee Related
  • 1989-11-09 CA CA002002578A patent/CA2002578C/fr not_active Expired - Fee Related
  • 1989-11-10 BR BR898905751A patent/BR8905751A/pt not_active IP Right Cessation
  • 1989-11-10 MX MX018315A patent/MX174375B/es unknown
• 1996
  • 1996-06-19 GR GR960401654T patent/GR3020275T3/el unknown

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